Block copolymer

ABSTRACT

Block copolymer comprising at least two kinds of polymer components each having a different structural unit in the polymer selected from polyamide, polyester, polycarbonate and polyarylate. The present block copolymer has a distinguished moldability and can be produced even from rework products or recycle products in a simple and economical manner.

TECHNICAL FIELD

[0001] The present invention relates to a block copolymer, and moreparticularly to a block copolymer with a distinguished moldability,which can be simply and economically produced even from rework productsor recycle products, and which is also capable of producing moldingsdistinguished in rigidity at high temperatures, heat resistance,chemical resistance, surface appearance, etc.

BACKGROUND ART

[0002] Polyamides, polyesters, polycarbonates and polyarylates are knownas engineering plastics and are widely used as materials for variousparts in the versatile consumer goods fields including packaging,containers, etc., the automobile field, the electric and electronicfield, the machinery and industrial product field, the office-equipmentfield, the aviation and space development field, etc.

[0003] To attain higher integration and higher weight, demands forsubstituting engineering plastics for metallic materials have beenrecently much intensified in these various fields of part materials, andas a result the performance level required for the engineering plasticshas been made much higher. Specifically, resin materials having anappearance substitutable for the metallic materials and applicable tosevere circumstances such as excessive exposure to heat, light,chemicals, etc. have been keenly desired. From the environmentalviewpoint, on the other hand, the spur to reuse moldings and parts ofthe engineering plastics as rework or recycle products has been alsointensified.

[0004] To meet these intensified demands for the engineering materialcharacteristics, methods for blending mixtures of different kinds ofresin components with a compatibilizing agent by melt kneading, that is,polymer alloy technology, have been so far studied to improve theirperformances while making up for disadvantages of single resinmaterials. It is well known that the materials based on the polymeralloy technology have been already commercially available.

[0005] However, in improvement of the compatibility of different kindsof thermoplastic resins, the polymer alloy technology still suffers fromeconomical problems such as requirements for special compatibilizingagents and for modification of molecular structures of resins per se.

[0006] To overcome the above-mentioned problems, a more economical andeasier method than the polymer alloy technology, that is, a method usingmixtures of different kinds of resin components together with a reactioncatalyst has been now under study. Specifically, U.S. Pat. No. 4,417,032discloses a method for producing a somewhat random copolymer bymelt-blending two or more kinds of homopolymers of polyamide in thepresence of a phosphite ester compound. U.S. Pat. No. 4,417,031discloses a method for producing graft and/or block copolymers byreaction of two or more kinds of homopolymers of polyamide, polyesterand β-unsaturated carboxylic acid. JP-A-6-62846 discloses a method formelt-blending polyamide with polyester in the presence of anarylphosphoryl azide compound. Japanese Patent No. 2,721,479 discloses aresin composition comprising a mixture of polybutylene terephthalatehaving a specific viscosity with polyester, and a specific phosphoruscompound. Furthermore, Japanese Patent No. 2,999,546 discloses a methodfor adjusting a melt flow rate by mixing a mixture of at least two kindsof thermoplastic resins selected from polyamide, polyester, polyarylate,etc. with a filler such as glass fibers, etc. followed by melt kneadingunder reduced pressure.

DISCLOSURE OF THE INVENTION

[0007] All of the above-mentioned prior arts comprise controlling thecompatibility of resin mixtures on the basis of exchange reactions ofpolyamide-polyamide, polyamide-polyester, polyester-polycarbonate, etc.According to the present inventors' study, control of the exchangereactions has not yet been satisfactory, so that the intensified demandsfor the engineering material characteristics in various uses have notbeen satisfied. It is under the present status that their developmentinto various uses is considerably restricted.

[0008] The present invention has been established to overcome theabove-mentioned problems, and an object of the present invention is toprovide a block copolymer having a distinguished moldability for formingvarious parts, etc., and which is producible from rework products orrecycle products as raw materials and also capable of producing moldingsdistinguished in rigidity at high temperatures, heat resistance,chemical resistance, surface appearance, etc.

[0009] As a result of intensive studies to attain the object of thepresent invention, the present inventors have successfully found thatthe object of the present invention can be attained by using a blockcopolymer comprising specific polymer components and having a specificrelation between the glass transition temperatures of the individualpolymer components and the glass transition temperature of the resultingblock copolymer, and have established the present invention.

[0010] That is, the present invention includes the following aspects[1]-[18] of the invention.

[0011] [1] A block copolymer, which comprises at least two kinds ofpolymer components each having a different structural unit in thepolymer, where the polymer components are selected from the groupconsisting of polyamide, polyester, polycarbonate and polyarylate, Ygiven by the following formula (1) is 0.1-0.9:$Y = \left. {\frac{1}{m}\sum\limits_{j = 1}^{m}}\quad \middle| \frac{{Tg}_{j} - X}{{Tg}_{j}^{(A)} - X} \right|$

[0012] (wherein m is the number of glass transition temperatures of theblock copolymer, Tg_(j) is the glass transition temperature (° C.) ofthe block copolymer, Tg^((A)) _(j) is the glass transition temperature(° C.) of the polymer component nearest to Tg_(j) among the glasstransition temperatures of the polymer components, and X is given by thefollowing formula (2):$X = {\sum\limits_{i = 1}^{n}{{Tg}^{(B)}{iw}_{i}}}$

[0013] wherein n is the number of polymer components, Tg^((B)) _(i) isthe glass transition temperatures (° C.) of the individual polymercomponents and w_(i) is the weight ratios of the individual polymercomponents).

[0014] [2] A block copolymer as described in said [1], wherein thedifference in the glass transition temperature between the polymercomponents constituting the block copolymer is 50° C. or higher.

[0015] [3] A block copolymer as described in said [1], wherein the blockcopolymer has a weight average molecular weight (Mw) of 20,000-200,000.

[0016] [4] A block copolymer as described in said [1], wherein the blockcopolymer comprises at least two kinds of polyamides.

[0017] [5] A block copolymer as described in said [1], wherein the blockcopolymer comprises polyamide and polyester.

[0018] [6] A block copolymer as described in said [1], wherein the blockcopolymer comprises at least two kinds of polyesters.

[0019] [7] A block copolymer as described in said [1], wherein the blockcopolymer comprises polyester and polycarbonate.

[0020] [8] A block copolymer as described in said [1], wherein thepolyamide is selected from the group consisting of polycaprolactam,polyhexamethylene adipamide, polyhexamethylene dodecamide,polyhexamethylene isophthalamide, polyhexamethylene terephthalamide,polyhexamethylene cyclohexylamide and their copolymers.

[0021] [9] A block copolymer, as described in said [1], wherein thepolyester is selected from the group consisting of polyethyleneterephthalate, polytrimethylene terephthalate and polybutyleneterephthalate.

[0022] [10] A block copolymer, as described in said [1], wherein theblock copolymer has an average sequence length of 10-50 determined bynuclear magnetic resonance (¹³C—NMR).

[0023] [11] A process for producing a block copolymer, which comprisesmelt kneading (A) at least two kinds of polymer components each having adifferent structural unit in the polymer and selected from the groupconsisting of polyamide, polyester, polycarbonate and polyarylate, with(B) a phosphite ester compound and (C) a phosphite metal salt.

[0024] [12] A process for producing a block copolymer, as described insaid [11], wherein the polymer components (A) are at least two kinds ofpolyamides.

[0025] [13] A process for producing a block copolymer, as described insaid [11], wherein the polymer components (A) are polyamide andpolyester.

[0026] [14] A process for producing a block copolymer, as described insaid [11], wherein the polymer components (A) are at least two kinds ofpolyesters.

[0027] [15] A process for producing a block copolymer, as described insaid [11], wherein the polymer components (A) are polyester andpolycarbonate.

[0028] [16] A process for producing a block copolymer, as described insaid [11], wherein the proportion of the component (B) is 0.05-10 partsby weight and the proportion of the component (C) is 0.05-10 parts byweight on the basis of 100 parts by weight of the polymer components(A).

[0029] [17] A process for producing a block copolymer, as described insaid [11], wherein a molecular weight-controlling agent (D) is furthermelt kneaded.

[0030] [18] A process for producing a block copolymer, as described insaid [17], wherein the proportion of the component (D) is 0.05-10 partsby weight on the basis of 100 parts by weight of the polymer components(A).

BEST MODE FOR CARRYING OUT THE INVENTION

[0031] The block copolymer of the present invention comprises at leasttwo kinds of polymer components each having a different structural unitin the polymer. Further, the polymer components must be selected fromthe group consisting of polyamide, polyester, polycarbonate andpolyarylate.

[0032] The term “at least two kinds of polymer components each having adifferent structural unit in the polymer” means not only combinations ofdifferent polymer species such as polyamide and polyester or polyamideand polycarbonate, but also combinations of the same polymer speciessuch as polyamides themselves or polyesters themselves, so far asstructural units of the individual polymer species are different fromone another, because the latter can satisfy such requirements for thepresent invention as defined by the term “at least two kinds of polymercomponents each having a different structural unit in the polymer”. Forexample, when the polymer components are polyamide 66, whose structuralunits are hexamethylenediamine and adipic acid, and polyamide 6I, whosestructural units are hexamethylenediamine and isophthalic acid, both thepolyamide 66 and the polyamide 6I are included in such a definition ofthe present invention as given by the term “at least two kinds ofpolymer components each having a different structural unit in thepolymer” because the dicarboxylic acid components as the structuralunits are different from each other (e.g. adipic acid and isophthalicacid). Likewise, even if the copolymer components are polyamide 66,whose structural units are hexamethylenediamine and adipic acid,polyamide 6I, whose structural units are hexamethylenediamine andisophthalic acid, and polyamide 6, whose structural unit is caprolactam,they are included in such a definition as given by the term “at leasttwo kinds of polymer components each having a different structural unitin the polymer”.

[0033] Description will be made below of polyamide, polyester,polycarbonate and polyarylate as polymer components constituting thepresent block copolymer.

[0034] Polyamide for use in the present invention is not particularlylimited, so long as it is a polymer having an amide bond (—NHCO—) in themain chain, and can include, for example, polycaprolactam (polyamide 6),polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide(polyamide 66), polyhexamethylene sebacamide (polyamide 610),polyhexamethylene dodecamide (polyamide 612), polyundecamethyleneadipamide (polyamide 116), polyundecalactam (polyamide 11),polydodecalactam (polyamide 12), polytrimethylhexamethyleneterephthalamide (polyamide TMHT), polyhexamethylene isophthalamide(polyamide 6I), polynonanomethylene terephthalamide (polyamide 9T),polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylenecyclohexylamide (polyamide 6C), polybis(4-aminocyclohexyl)methanedodecamide (polyamide PACM 12), polybis(3-methylaminocyclohexyl)methanedodecamide (polyamidedimethyl PACM 12), polymetaxylylene adipamide(polyamide MXD6), polyundecamethylene hexahydroterephthalamide(polyamide 11T(H)), and polyamide copolymers comprising at least twokinds of different polyamides selected from the abovementionedpolyamides. Above all, preferable polyamides for attaining the object ofthe present invention include polycaprolactam (polyamide 6),polyhexamethylene adipamide (polyamide 66), polyhexamethylene dodecamide(polyamide 612), polyhexamethylene isophthalamide (polyamide 6I),polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylenecyclohexylamide (polyamide 6C), and polyamide copolymers comprising atleast two kinds of different polyamides selected from theabove-mentioned polyamides.

[0035] The molecular weight of the polyamide of the present inventionis, in terms of weight average molecular weight (Mw), preferably10,000-1,000,000, more preferably 15,000-500,000, most preferably20,000-200,000, from the viewpoints of moldability and mechanicalproperties of the resulting block copolymers. Weight average molecularweight can be determined by gel permeation chromatography (GPC), usinghexafluoroisopropanol (HFID) as a solvent and using polymethylmethacrylate (PMMA) as a molecular weight reference material.

[0036] Polyester for use in the present invention is not particularlylimited, so long as it is a polymer having an ester bond in the mainchain, and can include, for example, (i) aromatic polyester, (ii)polyester thermoplastic elastomer (iii) liquid crystal polyester, etc.

[0037] Aromatic polyester (i) is a thermoplastic polyester having anaromatic ring as a structural unit in the polymer, and includes, forexample, polymers or copolymers, obtained by condensation reaction of anaromatic dicarboxylic acid (or an ester-formable derivative) and a diol(or an ester-formable derivative) as the main components.

[0038] Aromatic dicarboxylic acid can include, for example, terephthalicacid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylicacid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid,3,3′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid,4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylicacid, 4,4′-diphenylisopropylidonedicarboxylic acid,1,2-bis-(phenoxy)ethane-4,4′-dicarboxylic acid,2,5-anthracenedicarboxylic acid, 4,4′-p-terphenylenedicarboxylic acid,2,5-pyridinedicarboxylic acid, etc. Above all, terephthalic acid andisophthalic acid are preferable.

[0039] Diol component can include, for example, aliphatic diols such asethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol,1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, diethyleneglycol, triethylene glycol, decamethylene glycol, etc.; alicyclic diolssuch as 1,4-cyclohexanedimethanol, etc.; and their mixtures. Long-chaindiols having a molecular weight of about 400—about 6,000 such aspolyethylene glycol, poly-1,3-propylene glycol, polytetramethyleneglycol, etc. or copolymers of their mixtures may be also used, so longas they are in a small proportion.

[0040] Aromatic polyester can include, for example, aromatic polyesterssuch as polyethylene terephthalate, polytrimethylene terephthalate,polybutylene terephthalate, polyhexamethylene terephthalate,polycyclohexanedimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene-2,6-naphthalene dicarboxylate,polyethylene-1,2-bis(phenoxy)ethane-4,4′-dicarboxylate, etc.; andaromatic polyester copolymers such as polyethyleneisophthalate/terephthalate, polybutylene isophthlate/terephthalate,polybutylene terephthalate/decanedicarboxylate, etc. Above all,polyethylene terephthalate, polytrimethylene terephthalate andpolybutylene terephthalate are preferable from the viewpoints ofmoldability and mechanical properties of the resulting block copolymers.

[0041] Polyester thermoplastic elastomer (ii) contains aromaticpolyester as a hard segment and poly(alkylene oxide) glycol and/oraliphatic polyester as a soft segment, and can include, for example,polyether-ester block copolymer, polyester-ester block copolymer,polyether-ester-ester copolymer, etc.

[0042] A ratio of aromatic polyester hard segment/soft segment in thepolyester thermoplastic elastomer is preferably 95/5-10/90 by weight,particularly 90/10-30/70 by weight.

[0043] Hard segment-constituting aromatic polyester is preferably apolymer obtained by polycondensation of dicarboxylic acid component,about 60% by mole or more of which is usually terephthalic acidcomponent, and diol component. It is preferable to use as otherdicarboxylic acid components than terephthalic acid and diol componentthose mentioned in reference to the aromatic polyester (i),specifically, for example, polyethylene terephthalate, polybutyleneterephthalate, polyethylene (terephthalate/isophthalate), polybutylene(terephthalate/isophthalate), etc. and their mixtures.

[0044] Soft segment-constituting poly(alkylene oxide) glycol andaliphatic polyester, on the other hand, can include, for example,polyethylene glycol, poly(1,2-and 1,3-propylene oxide) glycol,poly(tetramethylene oxide) glycol, copolymer of ethylene oxide andpropylene oxide, copolymer of ethylene oxide and tetrahydrofuran,polyethylene adipate, poly-ε-caprolactone, polyethylene sebacate,polybutylene sebacate, etc., and their mixtures.

[0045] Polyester thermoplastic elastomer can include, for example,polyethylene terephthalate.poly(tetramethylene oxide) glycol blockcopolymer, polyethylene terephthalate/isophthalate.poly(tetramethyleneoxide) glycol copolymer, polybutylene terephthalate.poly(tetramethyleneoxide) glycol block copolymer, polybutyleneterephthalate/isophthalate.poly(tetramethylene oxide) glycol blockcopolymer, polybutyleneterephthalate/decanedicarboxylate.poly(tetramethylene oxide) glycolblock copolymer, polyethylene terephthalate poly(propyleneoxide/ethylene oxide) glycol block copolymer, polybutyleneterephthalate.poly(propylene oxide/ethylene oxide) glycol blockcopolymer, polybutylene terephthalate/isophthalate.poly(propyleneoxide/ethylene oxide) glycol block copolymer, polybutyleneterephthalate/decanedicarboxylate.poly(propylene oxide/ethylene oxide)glycol block copolymer, polybutylene terephthalate.poly(ethylene oxide)glycol block copolymer, polyethylene terephthalate.poly(ethylene oxide)glycol block copolymer, polybutylene terephthalate.polyethylene adipateblock copolymer, polybutylene terephthalate polybutylene adipate blockcopolymer, polybutylene terephthalate.polybutylene sebacate blockcopolymer, polybutylene terephthalate.poly-ε-caprolactone blockcopolymer, etc.

[0046] Molecular weight of the aromatic polyester and polyesterthermoplastic elastomer is, in terms of weight average molecular weight(Mw), preferably 10,000-1,000,000, more preferably 15,000-500,000, mostpreferably 20,000-200,000, from the viewpoints of moldability andmechanical properties of the resulting block copolymers. Weight averagemolecular weight can be determined by gel permeation chromatography(GPC), using hexafluoroisopropanol as a solvent and polymethylmethacrylate (PMMA) as a molecular weight reference material.

[0047] Liquid crystal polyester (iii) is a polyester called“thermotropic liquid crystal polymer, which can form an anisotropic meltat a temperature of 400° C. or lower, and can include, for example,those based on combinations of aromatic dicarboxylic acid, aromatic dioland aromatic hydroxycarboxylic acid, combinations of different kinds ofaromatic hydroxycarboxylic acid, combinations of aromatic dicarboxylicacid and aromatic diol, those obtained by reaction of polyester such aspolyethylene terephthalate, etc. with aromatic hydroxycarboxylic acid,etc. In place of these aromatic dicarboxylic acid, aromatic diol andaromatic hydroxycarboxylic acid, ester-formable derivatives thereof maybe used in some cases.

[0048] Aromatic dicarboxylic acids represented by the following formulaecan be used.

[0049] Aromatic diols represented by the following formulae can be used.

[0050] Aromatic hydroxycarboxylic acids represented by the followingformulae can be used.

[0051] Molecular weight of liquid crystal polyester is, in terms ofweight average molecular weight, preferably 10,000-1,000,000, morepreferably 15,000-500,000, most preferably 20,000-200,000 from theviewpoints of moldability and mechanical properties of the resultingblock copolymers. Weight average molecular weight can be determined bygel permeation chromatography (GPC), using a solvent mixture ofhexafluoroisopropanol and pentafluorophenol (mixing ratio: 1/1 byweight) as a solvent and polymethyl methacrylate (PMMA) as a molecularweight reference material.

[0052] Polycarbonate for use in the present invention is selected fromaromatic homopolycarbonates and aromatic-aromatic copolycarbonates, andincludes, for example, those obtained by a phosgene process comprisinginjecting phosgene to a bifunctional phenolic compound in the presenceof a caustic alkali and a solvent or by a transesterification processcomprising conducting transesterification between the bifunctionalphenolic compound and carbonate diester in the presence of a catalyst.

[0053] The bifunctional phenolic compound is represented by thefollowing formula:

[0054] where R₁ and R₂ are hydrogen atoms, alkyls having 1-10 carbonatoms or halogen atoms, m and n show the numbers of substituents and areintegers of 0-4, and (Ar) shows one of the following formulae:

[0055] where R₃, R₄, R₅ and R₆ are hydrogen atoms, alkyls having 1 to 10carbon atoms or phenyls; R₃ and R₄ may be joined together to form aring; and R₁, R₂, R₃, R₄, R₅ and R₆ may be the same or different.

[0056] Bifunctional phenolic compound can include, for example,bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-methylphenyl)propane,1,1-bis(4-hydroxy-3-t-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(4-hydroxyphenyl)-cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4′-dihydroxydiphenyl ether,4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxyphenyl sulfide,4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide,4,4′-dihydroxydiphenylsulfone,4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and their mixtures. Aboveall, 2,2′-bis(4-hydroxyphenyl)propane, i.e. bisphenyl A or1,1-bis(4-hydroxyphenyl)cyclohexane is particularly preferable.

[0057] Carbonate diester can include, for example, diphenyl carbonate,ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate,dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate,dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.Above all, diphenyl carbonate is preferable.

[0058] Molecular weight of the aromatic polycarbonate of the presentinvention is, in terms of weight average molecular weight (Mw),preferably 10,000-1,000,000, more preferably 15,000-500,000, mostpreferably 20,000-200,000, from the viewpoints of moldability andmechanical properties of the resulting block copolymers. Weight averagemolecular weight can be determined by gel permeation chromatography(GPC), using chloroform as a solvent and polystyrene (PS) as a molecularweight reference material.

[0059] Polyarylate for use in the present invention is prepared by amelt polymerization process comprising reacting a bifunctional phenoliccompound with an aromatic dicarboxylic acid in a hot melt state, by asolution polymerization process comprising reacting a bifunctionalphenolic compound with an aromatic dicarboxylic acid dichloride in anorganic solvent in the presence of an amine as a deoxidant, by aninterfacial polymerization comprising dissolving a bifunctional phenoliccompound and an aromatic dicarboxylic acid dichloride into two kinds ofnon-intermiscible solvents and conducting polycondensation reaction atthe interface while mixing the two solutions in the presence of analkali by stirring, etc.

[0060] Bifunctional phenolic compound can be represented by thefollowing formula:

[0061] where R₁ and R₂ are hydrogen atoms, alkyls having 1 to 10 carbonatoms or halogen atoms; m and n show the numbers of substituents and areintegers of 0-4; and (A) are represented by the following formulae:

[0062] where R₃, R₄, R₅ and R₆ are hydrogen atoms, alkyls having 1 to 10carbon atoms or phenyls; R₃ and R₄ may be joined together to form aring; and R₁, R₂, R₃, R₄, R₅ and R₆ may be the same or different.

[0063] Bifunctional phenolic compound can include, for example,bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-methylphenyl)propane,1,1-bis(4-hydroxy-3-t-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4′-dihydroxydiphenyl ether,4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxyphenyl sulfide,4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide,4,4′-dihydroxydiphenyldiphenyl sulfoxide,4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide,4,4′-dihydroxydiphenylsulfone,4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, and their mixtures. Aboveall, 2,2-bis(4-hydroxyphenyl)propane, i.e. bisphenol A and1,1-bis(4-hydroxyphenyl)cyclohexane are preferable.

[0064] Aromatic dicarboxylic acid is not particularly limited, and caninclude, for example, terephthalic acid, isophthalic acid,naphthalenedicarboxylic acid, etc. or their mixtures, and alsoalkyl-substituted homologs and halides of these aromatic dicarboxylicacids or their mixtures.

[0065] Molecular weight of polyarylate is, in terms of weight averagemolecular weight (Mw), preferably 10,000-1,000,000, more preferably15,000-500,000, most preferably 20,000-200,000, from the viewpoints ofmoldability and mechanical properties of the resulting block copolymers.Weight average molecular weight can be determined by gel permeationchromatography (GPC), using chloroform as a solvent and polymethylmethacrylate (PMKA) as a molecular weight reference material.

[0066] In the present invention, preferable block copolymers include,for example, block copolymers comprising at least two kinds ofpolyamide, block copolymers comprising polyamide and polyester, blockcopolymers comprising at least two kinds of polyester and blockcopolymers comprising polyester and polycarbonate.

[0067] The present block copolymer must have a specific relation betweenglass transition temperatures of the individual polymer components andglass transition temperature of the resulting block copolymer. That is,in the following formula (1) showing a relation between glass transitiontemperatures of the individual polymer components and glass transitiontemperature of the resulting block copolymer, the present blockcopolymer must satisfy such conditions as Y is in a range of 0.1-0.9,preferably 0.15-0.85, most preferably 0.2-0.7:$Y = \left. {\frac{1}{m}\sum\limits_{j = 1}^{m}}\quad \middle| \frac{{Tg}_{j} - X}{{Tg}_{j}^{(A)} - X} \right|$

[0068] (where m is the number of glass transition temperatures of theblock copolymer, Tg_(j) is the glass transition temperature (° C.) ofthe block copolymer, Tg^((A)) _(j) is the glass transition temperature(° C.) of the polymer component nearest to Tg_(j) among the glasstransition temperatures of the individual polymer components, and X isgiven by the following formula (2):$X = {\sum\limits_{i = 1}^{n}{{Tg}^{(B)}{iw}_{i}}}$

[0069] where n is the number of polymer components, TG^((B)) _(i) is theglass transition temperatures of the individual polymer components andw_(i) is the ratios by weight of the individual polymer components).

[0070] Glass transition temperatures of the individual polymercomponents and block copolymers can be determined by differentialscanning calorimetory (DSC) according to JIS K7121, using samplesobtained by reducing contents of water, hydrophilic solvent and the liketo less than 0.1% by weight by drying and the like, or by a method fordetermining dependency of dynamic viscoelasticity on temperatureaccording to JIS k7198, or by M-DSC (Modulated-DSC).

[0071] The present block copolymer can have a single glass transitiontemperature in one case and a plurality of glass transition temperaturesin another case. Thus, the above-mentioned Tg^((A)) _(j), i.e. glasstransition temperature (° C.) of polymer component nearest to Tg_(j)(glass transition temperature of block copolymer) among the glasstransition temperatures of the individual polymer components can bedetermined from a relation between the value and number of glasstransition temperatures of the block copolymer in the following manner.

[0072] For example, when the block copolymer comprises a polymercomponent P (glass transition temperature Tg^((B)) ₁=40° C.) and apolymer component Q (glass transition temperature Tg^((B)) ₂=100° C.),and the block copolymer has one glass transition temperature (Tg₁=80°C.), the glass transition temperature Tg^((B)) ₂ (100° C.) of polymercomponent Q is the nearest to the glass transition temperature Tg₁ (80°C.) among the glass transition temperatures of polymer components P andQ, and thus Tg^((A)) ₁=100.

[0073] When the block copolymer comprises a polymer component P (glasstransition temperature Tg^((B)) ₁=40° C.) and a polymer component Q(glass transition temperature Tg^((B)) ₂=100° C.), and the blockcopolymer has two glass transition temperatures, i.e. Tg₁=50° C. andTg₂=80° C., respectively, glass transition temperature Tg^((B)) ₁ (40°C.) is the nearest to glass transition temperature Tg1 (50° C.) of theblock copolymer among the polymer components P and Q, and thus Tg^((A))₁=4° C., whereas glass transition temperature Tg^((B)) ₂ (100° C.) isthe nearest to glass transition temperature Tg₂ (80° C.) of the blockcopolymer, and thus Tg^((A)) ₂=100° C.

[0074] When Y is less than 0.1 in the above-mentioned formula (1), therigidity at high temperatures of the resulting moldings from the presentblock copolymers is liable to decrease, whereas above 0.9 the appearanceof the moldings is liable to be degraded.

[0075] In the present invention, it is preferable that at least twokinds of polymer components have a difference of 50° C. or more in theglass transition temperature between the polymer components. When thepresent block copolymer comprises polymer components having a differenceof less than 50° C. in the glass transition temperature therebetween,the rigidity at high temperatures and heat resistance of the resultingmoldings are not thoroughly improved in some cases.

[0076] Molecular weight of the present block copolymer is, in terms ofweight average molecular weight (Mw), preferably 20,000-200,000, morepreferably 25,000-150,000, most preferably 30,000-150,000, from theviewpoints of moldability and mechanical properties. Weight averagemolecular weight can be determined by gel permeation chromatography(GPC), using one kind of solvent selected from chloroform,hexafluoroisopropanol and pentafluorophenol or a solvent mixture of atleast two of these solvents as a solvent and polystyrene (PS) orpolymethyl methacrylate (PMMA) as a molecular weight reference material.

[0077] The present block copolymer has an average sequence length ofpreferably 10-50, more preferably 15-50, much more preferably 20-50,most preferably 30-50, as determined by nuclear magnetic resonance(¹³C—NMR). The average sequence length can be calculated according to J.Polym. Sci. Phys. ED. Vol. 20, page 1875 (1982). It should be taken intoaccount that, when the average sequence length is less than 10, therigidity at high temperatures is liable to decrease, whereas above 50 apoor appearance is liable to be observed.

[0078] Dispersion state of the present block copolymer can be observedby an electron microscope. For example, a microsection adjusted by dyefixation, using osmium tetroxide and/or ruthenium tetroxide, ifrequired, can be observed by a transmission electron microscope (TEM),or a sample pretreated by an appropriate solvent capable of dissolvingonly the dispersed phase can be also observed by a scanning electronmicroscope (SEM).

[0079] Average particle size of the dispersed phase is preferably0.01-30 μm, more preferably 0.01-10 μm. When the average particle sizeis outside the above-mentioned range, a decrease in the rigidity at hightemperatures and poor appearance of moldings obtained from the blockcopolymer are more liable to take place. The average particle size canbe calculated in the following manner. A section cut away from the blockcopolymer or the moldings is photographed. Then, diameter di and numberni of particles of dispersed phase are determined. Then, the averageparticle size is calculated by the following equation:

Average particle size=Σdi·ni/Σni

[0080] where when the particle is not in a spherical shape, length ofits major axis and length of its minor axis should be measured, andone-half of the sum total of both lengths should be referred to asparticle size. In the calculation of average particle size, at least 100particle sizes must be measured.

[0081] Description will be made below of a process for producing thepresent block copolymer. The process is not particularly limited, andany process can be used, so long as the resulting block copolymers cansatisfy the condition that Y is in a range of 0.1-0.9 in theabove-mentioned formula (1).

[0082] However, a preferable process is that which comprises meltkneading (A) at least two kinds of polymer components each having adifferent structural unit in the polymer and selected from the groupconsisting of polyamide, polyester, polycarbonate and polyarylate with(B) a phosphite ester compound and (C) a phosphite metal salt or aphosphate metal salt.

[0083] A more preferable process is that which comprises melt kneading(A) at least two kinds of polymer components each having a differentstructural unit in the polymer and selected from the group consisting ofpolyamide, polyester, polycarbonate and polyarylate with (B) a phosphateester compound and (C) a phosphite metal salt. The most preferableprocess is that which comprises (A) melt kneading (A) at least two kindsof polymer components each having a different structural unit in thepolymer and selected from the group consisting of polyamide, polyester,polycarbonate and polyarylate with (B) a phosphite ester compound, (C) aphosphite metal salt and (D) a molecular weight-controlling agent.

[0084] It should be taken into account that, when only a phosphate metalsalt is used as Component (C), color tone deterioration and a decreasein the rigidity at high temperatures are liable to take place.

[0085] Phosphite ester compound (B) of the present invention can berepresented by the following general formula:

(OR)_(n)P(OH)_(3−n)

[0086] where R is an alkyl, a phenyl or a substituted alkyl, where partof the alkyl is replaced with a hydrocarbon group, etc.; n is 1, 2 or 3;and (OR) group may be the same or different.

[0087] R can include, for example, aliphatic groups such as methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl,n-octyl, 2-ethylhexyl, decyl, lauryl, tridecyl, stearyl, oleyl, etc.;aromatic groups such as phenyl, biphenyl, etc.; aromatic groups, etc.with a substituent such as hydroxy, methyl, ethyl, propyl, t-butyl,nonyl, methoxy, ethoxy, etc.

[0088] Preferable phosphite ester compounds include, for example, ethylphosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite,diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropylphosphite, tributyl phosphite, trioctyl phosphite, tributoxyethylphosphite, tris(2-ethylhexyl)phosphite, triphenyl phosphite,diphenylcresyl phosphite, tricresyl phosphite, biphenyl phosphite,tris(2,4-di-t-butylphenyl)phosphite,tris(1,5-di-t-butylphenyl)phosphite, tris(dimethylphenyl)phosphite,tris(isopropylphenyl)phosphite, octyldiphenyl phosphite, and theirmixtures.

[0089] The content of the phosphite ester compound is preferably 0.05-10parts by weight, more preferably 0.1-5 parts by weight, most preferably0.5-2.5 parts by weight, on the basis of 100 parts by weight of thetotal of the polymer components (A). When the content is less than 0.05parts by weight, the desired improvement effect of the present inventionsometimes cannot be obtained, whereas above 10 parts by weight theextrudibility or molding processability is liable to decrease.

[0090] Phosphite metal salt (C) of the present invention includes metalsalts of phosphorous acid and hypophosphorous acid with such metals aselements of Groups 1, 2, 3, 4, 5, 6, 7, 8, 11, 12 and 13 of the PeriodicTable, and tin, lead, etc. These phosphite metal salts can be used aloneor in combination of at least two thereof.

[0091] From the viewpoint of remarkably attaining the object of thepresent invention, preferable is a hypophosphite metal salt and mostpreferable are sodium hypophosphite (NaH₂PO₂.H₂O) and calciumhypophosphite (Ca(H₂PO₂)₂) or their mixture among them.

[0092] The content of the phosphite metal salt is preferably 0.05-10parts by weight, more preferably 0.1-5 parts by weight, most preferably0.5-2.5 parts by weight, on the basis of 100 parts by weight of thetotal of the polymer components (A). When the content is less than 0.05parts by weight, the desired improvement effect of the present inventionsometimes cannot be obtained, whereas above 10 parts by weight theextrudibility or molding processability is liable to decrease.

[0093] When the phosphite ester compound (B) and the phosphite metalsalt (C) are melt kneaded together in the production of the presentblock copolymer, the phosphite ester compound (B) and the phosphitemetal salt (C) are incorporated into the block copolymer, but the stateof occurrence of the phosphite ester compound (B) and the phosphitemetal salt (C) in the melt kneaded block copolymer is not particularlylimited. For example, the phosphite ester or phosphite metal salt may befound therein as they are or in the state of a phosphate ester orphosphate metal salt, or in a mixed state thereof, or in a hydrolyzedstate of the phosphite ester compound or phosphite metal salt, forexample, in a state of phosphorous acid, phosphoric acid or the like.

[0094] Molecular weight-controlling agent (D) of the present inventioncan include, for example, water, monocarboxylic acids such as aceticacid, stearic acid, etc.; dicarboxylic acids such as adipic acid,isophthalic acid, terephthalic acid, etc.; monoamines such asstearylamine, etc.; diamines such as hexamethylenediamine, etc.;carboxylic acid metal salts such as sodium acetate, calcium acetate,calcium stearate, etc., and their mixtures.

[0095] The content of the molecular weight-controlling agent ispreferably 0.05-10 parts by weight, more preferably 0.1-5 parts byweight, most preferably 0.5-2.5 parts by weight, on the basis of 100parts by weight of the total of the polymer components (A). When thecontent is less than 0.05 parts by weight, the desired improvementeffect of the present invention sometimes cannot be obtained, whereasabove 10 parts by weight, the extrudibility and molding processabilityare liable to decrease.

[0096] A method for melt kneading the polymer components (A) with thephosphite ester component (B), the phosphite metal salt (C) and themolecular weight-controlling agent (D) is not particularly limited, andcan include, for example, a method for kneading all the components atthe same time, a method for kneading prekneaded blends, such as a methodfor melt kneading a prekneaded mixture of the polymer components withthe phosphite ester compound and the phosphite metal salt together; amethod for successively feeding the individual components on the wayalong an extruder, such as a method for successively feeding thephosphite ester compound, the phosphite metal salt, the molecularweight-controlling agent, etc. to the polymer components, on the wayalong the extruder, or combinations of these methods.

[0097] Any well known apparatus for carrying out melt kneading can beused. For example, melt kneaders such as a monoaxial or biaxialextruder, a Banbury mixer, mixing rolls, etc. are preferable. Above all,a biaxial extruder with a degassing mechanism (vent) and side feeders ismost preferable.

[0098] Preferable conditions for melt kneading are a pressure reductiondegree of about 0-about 0.07 Mpa, a kneading temperature of about1-about 100° C. higher than the melting point or softening point of thepolymer components determined by differential scanning calorimetry (DSC)according to JIS K7121, a kneader shearing speed of about 100 (sec⁻¹) orhigher and an average kneader retention time of about 1-about 15minutes. It should be taken into account that when the conditions areoutside the above-mentioned ranges, lowering of the productivity andmolding process-ability, unsatisfactory appearance of the resultingmoldings and unsatisfactory improvement effect on the physicalproperties are sometimes liable to occur.

[0099] The present block copolymer can contain an oxide or a peroxide,which can include, for example, oxides or peroxides of elements of Group1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 14 and 15 of the Periodic Table, ortheir mixtures. Preferable are oxides of Group 2, such as CaO, etc.;oxides of Group 4 such as TiO₃, ZrO₂, etc., oxides of Group 6 such asCrO₃, MoO₃, WO₃, etc.; oxides of Group 12 such as ZnO, etc.; oxides ofGroup 13 such as B₂O₃, Al₂O₃, etc.; oxides of Group 14 such as SiO₂,GeO₂, etc.; oxides of Group 15 such as Sb₂O₃, etc.; and oxides of Group8 such as Fe₂O₃, Fe₃O₄, CoO, NiO, Cu₂O, etc.

[0100] The present block copolymer can contain a moldability-improvingagent. The moldability-improving agent is at least one compound selectedfrom compounds consisting of higher fatty acids, higher fatty acidesters, higher fatty acid amide compounds, polyalkylene glycols or theirterminal-modified derivatives, low molecular weight polyethylene oroxidized low molecular weight polyethylene, substitutedbenzylidenesorbitol, polysiloxane, caprolactones and inorganic crystalnucleating agents.

[0101] The present block copolymer can further contain a deteriorationinhibitor to prevent heat deterioration and coloring when heated and toimprove heat aging resistance and weather resistance. The deteriorationinhibitor is at least one compound selected from a phenolic stabilizersuch as hindered phenol compounds, etc.; a phosphite-based stabilizer, ahindered amine-based stabilizer, a triazine-based stabilizer and asulfur-based stabilizer.

[0102] The present block copolymer can contain a coloring agent. Thecoloring agent is at least one coloring agent selected from dyes such asNigrosine, etc.; pigments such as titanium oxide, carbon black, etc.;metallic particles of aluminum, colored aluminum, nickel, tin, copper,gold, silver, platinum, iron oxide, stainless steel, titanium, etc.; andmetallic pigments such as mica pearl pigments, color graphite, colorglass fibers, color glass flakes, etc.

[0103] The present block copolymer can contain electroconductive carbonblack. The electroconductive carbon black is at least one kind of carbonblack selected from acetylene black, Ketjen black, carbon nonatube, etc.Above all, those with a good chain structure and with a high aggregationare preferable.

[0104] The present block copolymer can contain a flame retardant.Preferable flame retardant is a non-halogen-based flame retardant or abromine-based flame retardant.

[0105] The non-halogen-based flame retardant is at least one flameretardant selected from a phosphorus-based flame retardant such as redphosphorus, ammonium phosphate, ammonium polyphosphate, etc.; a metalhydroxide or an inorganic metal compound hydrate such as aluminumhydroxide, magnesium hydroxide, dolomite, hydrotalcite, calciumhydroxide, barium hydroxide, basic magnesium carbonate, zirconiumhydroxide, tin hydroxide, zinc hydroxide, hydroxy zinc stannate, etc.,an inorganic compound-based flame retardant of boric acid compounds suchas zinc borate, zinc metaborate, barium metaborate, etc.; atriazine-based flame retardant such as melamine, melam, melem, mellon(product obtained from 3 molecules of melem by trimoleculardeammoniation at 300° C. or higher), melamine cyanurate, melaminephosphate, melamine polyphosphate, succinoguanamine, adipoguanamine,methylglutaroguanamine, melamine resin, etc.; and a silicone-based flameretardant such as silicone resin, silicone oil, silica, etc.

[0106] The bromine-based flame retardant is at least one flame retardantselected from compounds selected from brominated polystyrene, brominatedpolyphenylene ether, brominated bisphenol type epoxy polymers andbromine-based cross-linked aromatic polymers.

[0107] The present block copolymer can contain other polymer componentsthan polyamide, polyester, polycarbonate and polyarylate. Preferableother polymer components are at least one polymer component selectedfrom polyphenylene ether resin, polyoxymethylene resin, polyarylenesulfide resin, polyolefin resin, styrene resin, acrylic resin andrubber.

[0108] The present block copolymer can contain an inorganic filler. Theinorganic filler is at least one inorganic filler selected from glassfibers, carbon fibers, wollastonite, talc, mica, kaolin, barium sulfate,calcium carbonate, apatite, sodium phosphate, fluorite, silicon nitride,potassium titanate, molybdenum disulfide, etc.

[0109] The present block copolymer has a good moldability and thus canbe satisfactorily molded by well known molding methods such as wellknown plastic molding methods, for example, press molding, injectionmolding, gas-assisted injection molding, weld molding, extrusionmolding, blow molding, film molding, inflation molding, multilayermolding, expansion molding, melt spinning, etc.

[0110] Furthermore, the present block copolymer can be produced evenfrom rework products or recycle products as raw materials and thusrecyclic application of various moldings or parts, for example, recyclicapplication of recovered polyethylene terephthalate (PET) can beconducted.

[0111] Furthermore, moldings obtained from the present block copolymerare more distinguished in rigidity at high temperatures, heatresistance, chemical resistance, surface appearance, weather resistance,heat aging resistance, etc. than those obtained from the conventionalresin compositions and thus their application to automobile parts,electronic and electric parts, industrial machinery parts, various gearsand various parts of extrusion use, etc. is a beneficial advantage ofthe invention.

EMBODIMENTS

[0112] The present invention will be described in detail below,referring to embodiments, which are not restrictive of the presentinvention, and the present invention shall be construed within the scopeand spirit herein disclosed. Evaluation of physical properties in thefollowing Examples and Comparative Examples was made as follows:

1. Characteristics of Polymer Components and Block Copolymers

[0113] (1-1) Melting Point (° C.) Determined according to JIS K7121,using Perkin-Elmer DSC-7 type as a measuring apparatus by keeping about8 mg of a sample at 300° C. for 2 minutes in a nitrogen atmosphere, andthen cooling it down to 40° C. at a cooling rate of 20° C./min.,followed by keeping the sample at 40° C. for 2 minutes, and determininga melting point from the exothermic peak (melting peak) temperature,appearing when reheated at a heating rate of 20° C./min. as measurementconditions.

[0114] (1-2) Glass transition temperature (° C.)

[0115] Determined according to JIS K7121, using Perkin-Elmer DSC-7 typeas a measuring apparatus by melting a sample on a hot stage (MettlerEP80) at first and quenching the melt sample in liquid nitrogen, therebysolidifying it as a sample for the measurement, and then heating 10 mgof the sample for the measurement to a range of 30°-300° C. at a heatingrate of 20° C./min., thereby determining a glass transition temperature.

[0116] (1-3) Weight Average Molecular Weight (Mw)

[0117] Determined by gel permeation chromatography (GPC), using anapparatus HLC-8020, made by Tosoh Corp., a differential refractometer(RI) as a detector, at least one kind or a mixture of two or moresolvents selected from chloroform, hexafluoroisopropanol andpentafluorophenol as a solvent, and two columns of TSK gel-GMHHR-H andone column of G1000HHR, made by Tosoh Corp. Solvent flow rate was 0.6ml/min., sample concentration was 1-3 (mg sample)/1 (ml solvent), andinsoluble matters were removed from a sample by filtration through afilter to obtain a sample for the measurement. Weight average molecularweight (Mw) was calculated from the resulting elution curve, usingpolystyrene (PS) or polymethyl methacrylate (PMMA) as a molecular weightreference material.

[0118] (1-4) Average Sequence Length

[0119] Determined by ¹³C—NMR, using FT-NMR, model DPZ-400, made byBruker Corp., and d-sulfuric acid, d-hexafluoroisopropanol ord-chloroform as a solvent. Temperature was 25° C., sample concentrationwas 2 (mg sample)/10 (ml solvent), and tetramethylsilane (TMS) was usedas a chemical shift basis. Measurement was made under such conditions asnumber of accumulation about 20,000 and waiting period: 3.0 sec. Averagesequence length was calculated according to J. Polym. Sci. Phys. ED.Vol. 20, page 1875 (1982).

[0120] (1-5) Moisture Content (% by Weight)

[0121] Determined by Karl Fisher method, using 0.7 g of a sample for themeasurement in a moisture vaporizer (Model VA-06, made by MitsubishiChemical Corp.) at a temperature of 185° C.

2. Preparation of Physical Properties of Moldings

[0122] Moldings were prepared from block copolymers by an injectionmolding machine Model PS40E, made by Nissei Jushi K. K. at a moldtemperature of 80° C. under injection molding conditions of injectiontime: 17 sec. and cooling time: 20 sec. Cylinder temperature was set toa temperature of about 15°-40° C. higher than the melting points ofblock copolymers determined according to the conditions of said (1-1).

[0123] (2-1) Flexural Modulus and Flexural Strength (Mpa)

[0124] Determined according to ASTM D790.

[0125] (2-2) Tensile Strength (Mpa) and Tensile Elongation (%)

[0126] Determined according to ASTM D638.

[0127] (2-3) Notched Izod Impact Strength (J/m)

[0128] Determined according to ASTM D256.

[0129] (2-4) Surface Appearance

[0130] Gs 60° C. was measured according to JIS K 7150, using a handyglossmeter, model IG320, made by Horiba Seisakusho K. K.

[0131] (2-5) Color Tone (Value b)

[0132] Value b was determined by a color comparator Model ND-300A, madeby Nihon Denshoku K. K. The smaller the value b, the better the colortone.

[0133] (2-6) Development State of Environmental Stress Cracks

[0134] An injection-molded test piece immersed in hot water at 80° C.for 4 hours was kept in a bent state under a constant stress of 75 Mpaand its surface was coated with an aqueous 30 wt. % calcium chloridesolution. The test piece was left standing at 100° C. for 2 hours, andthen the crack development state of the test piece was observed.

[0135] (2-7) Water Absorption (wt. %)

[0136] Molded test piece was immersed in water at 23° C. for 24 hoursand water absorption was determined from a weight increment.

EXAMPLE 1

[0137] 100 Parts by weight of polymer components consisting of 70 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.,(moisture content: 0.08 wt. %), abbreviated to “PA66” in the followingTables) and 30 parts by weight of polyamide 6I (T40, made by Bayer,(moisture content: 0.01 wt. %), abbreviated to “PA6I” in the followingTables) were blended with 1.0 part by weight of tridecyl phosphite, 0.5parts by weight of calcium hypophosphite and 0.5 parts by weight ofadipic acid. Then, the blend was melt kneaded by a biaxial extruder(model TEM 35, made by Toshiba Machine Co., Ltd., biaxial,unidirectional screw-rotary type, L/D=47.6 (D=37 mm in diameter), whilefeeding 100 parts by weight of short glass fibers (JA416, made by AsahiFiber Glass Co., Ltd., abbreviated to “GF” in the following Tables)through a side feeder on the basis of 100 parts by weight of the polymercomponents. Extrusion was conducted at a screw revolution rate of 300rpm, a cylinder temperature of 280° C. (at a polymer temperature of 290°C. around the tip end nozzle), and a rate of 60 kg/hr (for a retentiontime of 2 minutes) without pressure reduction. Strand-formed polymer wasdischarged through the tip end nozzle, followed by water cooling andcutting to make pellets. The pellets were dried in a nitrogen atmosphereat 80° C. for 24 hours.

[0138] Glass transition temperature Tg^((B)) ₁ of polyamide 66 was 47.0°C., and glass transition temperature Tg^((B)) ₂ of polyamide 6I was 130°C., and parameter X=(47.0×0.7)+(130×0.3)=71.9° C. was calculatedtherefrom. Number of glass transition temperature of the resulting blockcopolymer pellets was one (m=1) and its value (Tg₁) was 62.0° C. Thus,among the glass transition temperatures of polyamide 66 and polyamide6I, the glass transition temperature of polyamide 66 is nearer to theglass transition temperature of the block copolymer, i.e. Tg^((A))₁=47.0° C., and thus parameter Y=|Tg₁−X|/|Tg^((A))₁−X|=|62.0-71.91|/|47.0-71.9|=0.40 was calculated therefrom. Evaluationresults of the resulting molding are shown in Table 1.

EXAMPLE 2

[0139] 100 Parts by weight of polymer components consisting of 60 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.,moisture content 0.08 wt. %)) and 40 parts by weight of polyamide 6I(T40, made by Bayer (moisture content: 0.01 wt. %) were blended with 1.0part by weight of tridecyl phosphite, 0.5 parts by weight of calciumhypophosphite and 0.5 parts by weight of adipic acid. Block copolymerpellets were prepared thereafter by the same operations as in Example 1.Characteristics of polymer components and block copolymer and evaluationresults of the resulting molding are shown in Table 1.

EXAMPLE 3

[0140] 100 Parts by weight of polymer components consisting of 70 partsby weight of water absorption-treated polyamide 66 (Leona 1300, made byASAHI KASEI Corp., (moisture content: 1.0 wt. %)) and 30 parts by weightof polyamide 6I (T40, made by Bayer (moisture content: 0.01 wt. %) wereblended with 1.0 part by weight of tridecyl phosphite and 0.5 parts byweight of calcium hypophosphite. The blend was melt kneaded by a biaxialextruder (model TEM35, made by Toshiba Machine Co., Ltd., biaxial,unidirectional screw-rotary type, L/D=47.6 (D=37 mm in diameter)), whilefeeding 100 parts by weight of short glass fibers (JA416, made by AsahiFiber Glass Co., Ltd.) through a side feeder on the basis of 100 partsby weight of the polymercomponents. Extrusion was conducted at a screwrevolution rate of 300 rpm, a cylinder temperature of 280° C. (at apolymer temperature of 290° C. around the tip end nozzle), a rate of 60kg/hr. (for a retention time of 2 minutes), and a pressure reductiondegree of 0.04 MPa. Strand-formed polymer was discharged through the tipend nozzle, followed by water cooling and cutting to make pellets. Thepellets were dried in a nitrogen atmosphere at 80° C. for 24 hours.Characteristics of polymer components and block copolymer and evaluationresults of the resulting molding are shown in Table 1.

COMPARATIVE EXAMPLE 1

[0141] 100 Parts by weight of polymer components consisting of 60 partsby weight of polyamide 66 (Leona 130, made by ASAHI KASEI Corp.,(moisture content 0.08 wt. %)) and 40 parts by weight of polyamide 6I(T40, made by Bayer (moisture content: 0.01 wt. %)) were blended with0.5 parts by weight of calcium hypophosphite and 0.5 parts by weight ofadipic acid. Block copolymer pellets were prepared thereafter by thesame operations as in Example 1. Characteristics of polymer componentsand block copolymer and evaluation results of the resulting molding areshown in Table 1.

EXAMPLE 4

[0142] Block copolymer pellets were prepared in the same manner as inExample 1 except that triphenyl phosphite was used in place of tridecylphosphite. Characteristics of polymer components and block copolymer,and evaluation results of the resulting molding are shown in Table 2.

EXAMPLE 5

[0143] Block copolymer pellets were prepared in the same manner as inExample 1 except that tris(2,4-di-t-butylphenyl) phosphite was used inplace of tridecyl phosphate. Characteristics of polymer components andblock copolymer, and evaluation results of the resulting molding areshown in Table 2.

EXAMPLE 6

[0144] Block copolymer pellets were prepared in the same manner as inExample 1 except that zinc phosphite was used in place of calciumhypophosphite. Characteristics of polymer components and blockcopolymer, and evaluation results of the resulting molding are shown inTable 2.

EXAMPLE 7

[0145] Block copolymer pellets were prepared in the same manner as inExample 1 except that zinc phosphate was used in place of calciumhypophosphite. Characteristics of polymer components and blockcopolymer, and evaluation results of the resulting molding are shown inTable 2.

EXAMPLE 8

[0146] 100 Parts by weight of polymer components consisting of 70 partsby weight of polyamide 6 (SF1013A, made by Ube Industries, Ltd.(moisture content: 0.08 wt. %), abbreviated to “PA6” in the followingTables) and 30 parts by weight of polyamide 6I (T40, made by Bayer(moisture content: 0.01 wt. %)) were blended with 2.0 parts by weight oftris(2,4-di-t-butylphenyl)phosphite, 0.5 parts by weight of calciumhypophosphite and 0.5 parts by weight of adipic acid. Block copolymerpellets were prepared thereafter by the same operations as in Example 1.Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 3.

EXAMPLE 9

[0147] 10.5 Kg of an equimolar mixture of hexamethylenediamine-adipicacid and 4.5 kg of an equimolar mixture ofhexamethylenediamine-isophthalic acid were used as polyamide rawmaterials. An aqueous solution of the polyamide raw materials wascharged into a 70-l autoclave with a stirring device and heated from 50°C. up to about 150° C. with stirring after being thoroughly flushed withnitrogen at 50° C., where heating was continued while removing water tothe system outside so that the pressure in the autoclave may not exceedabout 0.2 Mpa. As a result, about 7 kg was removed. Then, heating wascontinuously carried out up to about 270° C. for about one hour whileremoving water to the system outside so that the pressure in theautoclave may not exceed about 1.77 Mpa. Then, the pressure was reducedto atmospheric pressure over about one hour, and the stirring wasdiscontinued. Strand-formed polymer was discharged through a nozzle atthe lower part, followed by water cooling and cutting to obtainpolyamide 66/6I random copolymerization polyamide with a moisturecontent of 0.4 wt. %.

[0148] 100 Parts by weight of polymer components consisting of 90 partsby weight of the resulting polyamide 66/6I random copolymer (abbreviatedto “PA66/6I” in the following Tables) and 10 parts by weight ofpolyamide 61 (T40, made by Bayer (moisture content: 0.01 wt. %)) wereblended with 2.0 parts by weight of tris(2,4-di-t-butylphenyl)phosphite,0.5 parts by weight of calcium hypophosphite and 0.5 parts by weight ofadipic acid. Block copolymer pellets were prepared thereafter by thesame operations as in Example 1. Characteristics of polymer componentsand block copolymer, and evaluation results of the resulting molding areshown in Table 3.

EXAMPLE 10

[0149] 100 Parts by weight of polymer components consisting of 64 partsby weight of water absorption-treated polyamide 66 (Leona 1300, made byASAHI KASEI Corp. (moisture content: 1.0 wt. %)), 27 parts by weight ofpolyamide 6I (T40, made by Bayer (moisture content: 0.01 wt. %)) and 9parts by weight of polyamide 6 (SF1013A, made by Ube Industries, Ltd.(moisture content: 0.08 wt. %)) were blended with 2.0 parts by weight oftris(2,4-di-t-butylphenyl)phosphite and 0.5 parts by weight of calciumhypophosphite. Block copolymer pellets were prepared thereafter by thesame operations as in Example 3. Characteristics of polymer componentsand block copolymer, and evaluation results of the resulting molding areshown in Table 3.

EXAMPLE 11

[0150] 100 Parts by weight of polymer components consisting of 70 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.(moisture content: 0.08 wt. %)) and 30 parts by weight of polyamide 6(SF1013A, made by Ube Industries, Ltd. (moisture content: 0.08 wt. %))were blended with 2.0 parts by weight oftris(2,4-di-t-butylphenyl)phosphite, 0.5 parts by weight of calciumhypophosphite and 0.5 parts by weight of adipic acid. Block copolymerpellets were prepared thereafter by the same operations as in Example 1.Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 3.

EXAMPLE 12

[0151] 100 Parts by weight of polymer components consisting of 70 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.(moisture content: 0.08 wt. %)) and 30 parts by weight of polyethyleneterephthalate (NEH-2050, made by Unitika, Ltd. (moisture content: 0.01wt. %), abbreviated to “PET” in the following Tables) were blended with2.0 parts by weight of tris(2,4-di-t-butylphenyl)phosphite and 0.5 partsby weight of calcium hypophosphite. The blend was melt kneaded by abiaxial extruder (model TEM35, made by Toshiba Machine Co., Ltd.,biaxial unidirectional screw-rotary type, L/D=47.6 (D=37mm indiameter)), while feeding 50 parts by weight of short glass fibers(JA416, made by Asahi Fiber Glass Co., Ltd.) through a side feeder onthe basis of 100 parts by weight of the polymer components. Extrusionwas carried out at a screw revolution rate of 300 rpm, a cylindertemperature of 280° C. (a polymer temperature of 290° C. around the tipend nozzle), and a rate of 60 kg/hr (for a retention time of 2 minutes)without pressure reduction. Strand-formed polymer was discharged throughthe tip end nozzle, followed by water cooling and cutting to makepellets. The pellets were dried in a nitrogen atmosphere at 80° C. for24 hours.

[0152] Glass transition temperature Tg^((B)) ₁ of polyamide 66=47.0° C.and glass transition temperature Tg^((B)) ₂ of polyethyleneterephthalate=81.0° C. Thus, parameter X=(47.0×0.7)+(81.0×0.3)=57.2° C.was calculated. Number of glass transition temperature of the resultingblock copolymer pellets was two (m=2), and the values were Tg₁=50.1° C.and Tg₂=73.1° C., respectively. Thus, among the glass transitiontemperatures of polyamide 66 and polyethylene terephthalate, the glasstransition temperature of polyamide 66 was nearer to the glasstransition temperature Tg₁ of the block copolymer, whereas the glasstransition temperature of polyethylene terephthalate was nearer to theglass transition temperature Tg₂ of the block copolymer. Thus, Tg^((A))₁=47.0° C. and Tg^((A)) ₂=81.0° C. Parameter Y=(1/m)×{(|Tg₁−X|/|Tg^((A))₁−X|)+(|Tg₂−X|/|Tg^((A)) ₂−X|)}=(1/2)×{(|50.1-57.2|/|47.0-57.2|)}+(73.1-57.2|/|81.0-57.2|)}=0.68 wascalculated.

[0153] Average sequence length determined by ¹³C—NMR, usingd-hexafluoroisopropanol as a solvent was 22.5. Evaluation results of theresulting molding are shown in Table 4.

EXAMPLE 13

[0154] 100 Parts by weight of polymer components consisting of 60 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.(moisture content: 0.08 wt. %)) and 40 parts by weight of polyethyleneterephthalate (NEH-2050, made by Unitika, Ltd. (moisture content: lessthan 0.01 wt. %) were blended with 2.0 parts by weight oftris(2,4-di-t-butylphenyl)phosphite and 0.5 parts by weight of calciumhypophosphite. Block copolymer pellets were prepared thereafter by thesame operations as in Example 12. Characteristics of polymer componentsand block copolymer, and evaluation results of the resulting molding areshown in Table 4.

EXAMPLE 14

[0155] 100 Parts by weight of polymer components consisting of 70 partsby weight of polyamide 66 (Leona 1300, made by ASAHI KASEI Corp.(moisture content 0.08 wt. %)) and 30 parts by weight of regeneratedpolyethylene terephthalate (powders of recycled beverage bottles(moisture content: less than 0.01 wt. %)) were blended with 2.0 parts byweight of tris(2,4-di-t-butylphenyl)phosphite and 0.5 parts by weight ofcalcium hypophosphite. Block copolymer pellets were prepared thereafterby the same operations as in Example 12. Characteristics of polymercomponents and block copolymer, and evaluation results of the resultingmolding are shown in Table 4.

EXAMPLE 15

[0156] Block copolymer pellets were prepared in the same manner as inExample 12 except that polytrimethylene terephthalate (CP-BR, made byShell (moisture content: less than 0.01 wt. %), abbreviated to “PTT” inthe following Tables) was used in place of polyethylene terephthalate(NEH-2050, made by Unitika, Ltd.). Characteristics of polymer componentsand block copolymer, and evaluation results of the resulting molding areshown in Table 4.

EXAMPLE 16

[0157] Block copolymer pellets were prepared in the same manner as inExample 12 except that polybutylene terephthalate (1401-X06, made byToray Industries, Inc. (moisture content: less than 0.01 wt. %),abbreviated to “PBT” in the following Tables) was used in place ofpolyethylene terephthalate (NEH-2050, made by Unitika, Ltd.).Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 5.

EXAMPLE 17

[0158] 100 Parts by weight of polymer components consisting of 50 partsby weight of polyethylene terephthalate (NEH-2050, made by Unitika, Ltd.(moisture content: less than 0.01 wt. %)) and 50 parts by weight ofpolytrimethylene terephthalate (CP-BR, made by Shell (moisture content:less than 0.01 wt. %)) were blended with 2.0 parts by weight oftris(2,4-di-t-butylphenyl)phosphite and 0.5 parts by weight of calciumhypophosphite. Block copolymer pellets were prepared thereafter in thesame manner as in Example 12. Characteristics of polymer components andblock copolymer, and evaluation results of the resulting molding areshown in Table 5.

COMPARATIVE EXAMPLE 2

[0159] Block copolymer pellets were prepared in the same manner as inExample 12 only from 100 parts by weight of polymer componentsconsisting of 50 parts by weight of polyethylene terephthalate(NEH-2050, made by Unitika, Ltd. (moisture content: less than 0.01 wt.%)) and 50 parts by weight of polytrimethylene terephthalate (CP-BR,made by Shell (moisture content: less than 0.01 wt. %)). Characteristicsof polymer components and block copolymer, and evaluation results of theresulting molding are shown in Table 5.

EXAMPLE 18

[0160] 100 Parts by weight of polymer components consisting of 30 partsby weight of polycarbonate (Iupilon S-2000, made by MitsubishiEngineering Plastic Co., Ltd., abbreviated to “PC” in the followingTables) and 70 parts by weight of polybutylene terephthalate (1401-X06,made by Toray Industries, Inc.) were blended with 0.5 parts by weight oftris(2,4-di-t-butylphenyl)-phosphite and 0.5 parts by weight of calciumhypophosphite. The blend was extruded by a biaxial extruder (modelTEM35, made by Toshiba Machine Co., Ltd., biaxial, unidirectionalscrew-rotary type, L/D=46.7 (D=37 mm in diameter)) under such conditionsas screw revolution rate: 300 rpm, cylinder temperature: 280° C.(polymer temperature around the tip end nozzle=290° C.), rate: 60 kg/hr(retention time: 2 minutes) and pressure reduction degree: 0.01 Mpa.Strand-formed polymer was discharged through the tip end nozzle,followed by water cooling and cutting to make pellets. The pellets weredried in a nitrogen atmosphere at 80° C. Average sequence lengthdetermined by ¹³C—NMR, using d-chloroform as a solvent was 35.0.Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 6.

EXAMPLE 19

[0161] 100 Parts by weight of polymer components consisting of 50 partsby weight of polycarbonate (Iupilon S-2000, made by MitsubishiEngineering Plastic Co., Ltd.) and 50 parts by weight of polybutyleneterephthalate (1401-X06, made by Toray Industries, Inc.) were blendedwith 0.5 parts by weight of tris(2,4-di-butylphenyl)phosphite and 0.5parts by weight of calcium hypophosphite. Block copolymer pellets wereprepared thereafter by the same operations as in Example 18.Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 6.

EXAMPLE 20

[0162] Block copolymer pellets were prepared in the same manner as inExample 18 except that polytrimethylene terephthalate (CP-BR, made byShell) was used in place of polybutylene terephthalate (1401-X06, madeby Toray Industries, Inc.). Characteristics of polymer components andblock copolymer, and evaluation results of the resulting molding areshown in Table 6.

EXAMPLE 21

[0163] 100 Parts by weight of polymer components consisting of 30 partsby weight of polycarbonate (Iupilon S-2000, made by MitsubishiEngineering Plastic Co., Ltd.) and 70 parts by weight of polybutyleneterephthalate (1401-X06, made by Toray Industries, Inc.) were blendedwith 0.5 parts by weight of tris(2,4-di-t-butylphenyl)phosphite and 0.5parts by weight of zinc phosphite. Block copolymer pellets were preparedthereafter by the same operations as in Example 13. Average sequencelength determined by ¹³C—NMR, using d-chloroform as a solvent was 12.5.Characteristics of polymer components and block copolymer, andevaluation results of the resulting molding are shown in Table 7.

COMPARATIVE EXAMPLE 3

[0164] Block copolymer pellets were prepared in the same manner as inExample 13 except that 100 parts by weight consisting of 30 parts byweight of polycarbonate (Iupilon S-2000, made by Mitsubishi EngineeringPlastic Co., Ltd.) and 70 parts by weight of polybutylene terephthalate(1401-Z06, made by Toray Industries, Inc.) was only used withoutblending with tris(2,4-di-t-butylphenyl)phosphite and calciumhypophosphite. Average sequence length determined by ¹³C—NMR, usingd-chloroform as a solvent was 4.5. Characteristics of polymer componentand block copolymer, and evaluation results of the resulting molding areshown in Table 7. TABLE 1 Example Example Example Comp. Ex. 1 2 3 1 (A)Polymer components 2 2 2 2 Number of polymer components: n Kind ofpolymer (1) PA66 (1) PA66 (1) PA66 (1) PA66 components (2) PA6I (2) PA6I(2) PA6I (2) PA6I Glass transition temp. of (1) 47.0 (1) 47.0 (1) 47.0(1) 47.0 polymer components (2) 130 (2) 130 (2) 130 (2) 130 (° C.)Mixing ratio of polymer (1) 0.7 (1) 0.6 (1) 0.7 (1) 0.6 components:W_(I) (2) 0.3 (2) 0.4 (2) 0.3 (2) 0.4 Parameter X (° C.) 71.9 80.2 71.980.2 (B) Kind of phosphite B-1 B-1 B-1 — ester compound Mixing ratio to100 parts 1.0 1.0 1.0 — by wt of polymer component (parts by wt.) (C)Kind of phosphite Ca hypo- Ca hypo- Ca hypo- Ca hypo- metal saltphosphite phosphite phosphite phosphite Mixing ratio to 100 parts 0.50.5 0.5 0.5 by wt of polymer component (parts by wt.) (D) Kind ofmolecular Adipic Adipic — Adipic weight controlling agent acid acid acidMixing ratio to 100 parts 0.5 0.5 — 0.5 by wt of polymer component(parts by wt.) (E) Kind of other mixing GF GF GF GF material Mixingratio to 100 parts 100 100 100 100 by wt of polymer component (parts bywt.) Characteristics of block 32000 32000 38000 40000 copolymer Weightaverage molecular wt. (Mw) Number of glass 1 1 1 2 transition temp.: mGlass transition temp. 62.0 68.0 63.0 52.0 (°C.) 128.5 Parameter Y 0.400.37 0.36 0.91 Melting point (° C.) 252 250 247 259 Physical propertiesof 15.0 15.0 15.0 15.0 molding Flexural modulus (23° C.) (Gpa) Flexuralmodulus 12.0 13.0 11.7 12.0 (80° C.) (Gpa) Tensile strength (Mpa) 230230 230 190 Tensile elongation (%) 6.5 6.5 6.5 5.5 Notched Izod impact90 90 90 75 strength (23° C.) (J/m) Appearance 75 75 75 35 Color tone(value b) −3.0 −3.0 −3.0 2.5 Water absorption 1.00 0.90 1.02 1.25 (23°C. × 24 hr) (wt. %)

[0165] TABLE 2 Example Example Example Example 4 5 6 7 (A) Polymercomponents 2 2 2 2 Number of polymer components: n Kind of polymer (1)PA66 (1) PA66 (1) PA66 (1) PA66 components (2) PA6I (2) PA6I (2) PA6I(2) PA6I Glass transition temp. of (1) 47.0 (1) 47.0 (1) 47.0 (1) 47.0polymer components (2) 130 (2) 130 (2) 130 (2) 130 (° C.) Mixing ratioof polymer (1) 0.7 (1) 0.7 (1) 0.7 (1) 0.7 components: W_(i) (2) 0.3 (2)0.3 (2) 0.3 (2) 0.3 Parameter X (° C.) 71.9 71.9 71.9 71.9 (B) Kind ofphosphite B-2 B-3 B-1 B-1 ester compound Mixing ratio to 100 parts 1.01.0 1.0 1.0 by wt of polymer component (parts by wt.) (C) Kind ofphosphite Ca hypo- Ca hypo- Ca hypo- Zn metal salt phosphite phosphitephosphite phosphate Mixing ratio to 100 parts 0.5 0.5 0.5 0.5 by wt ofpolymer component (parts by wt.) (D) Kind of molecular Adipic AdipicAdipic Adipic weight controlling agent acid acid acid acid Mixing ratioto 100 parts 0.5 0.5 0.5 0.5 by wt of polymer component (parts by wt.)(E) Kind of other mixing GF GF GF GF material Mixing ratio to 100 parts100 100 100 100 by wt of polymer component (parts by wt.)Characteristics of block 32000 32000 32000 32000 copolymer Weightaverage molecular wt. (Mw) Number of glass 1 1 1 1 transition temp.: mGlass transition temp. 62.0 62.0 61.0 60.0 (° C.) Parameter Y 0.40 0.400.44 0.48 Melting point (° C.) 252 252 254 255 Physical properties of15.0 15.0 15.0 15.0 polymer components Flexural modulus (23° C.) (Gpa)Flexural modulus 12.0 12.0 11.5 11.0 (80° C.) (Gpa) Tensile strength(Mpa) 230 230 220 215 Tensile elongation (%) 6.5 6.5 6.5 6.0 NotchedIzod impact 90 90 90 80 strength (23° C.) (J/m) Appearance 75 75 70 60Color tone (value b) −3.0 −3.0 −2.0 −1.0 Water absorption 1.00 1.00 1.101.20 (23° C. × 24 hr) (wt. %)

[0166] TABLE 3 Example Example Example Example 8 9 10 11 (A) Polymercomponents 2 2 2 2 Number of polymer components: n Kind of polymar (1)PA6 (1) PA66/ (1) PA66 PA66 6I components (2) PA6I (1) PA6I (2) PA6I (2)PA6 (3) PA6 Glass transition temp. of (1) 43.0 (1) 67.0 (1) 47.0 (1)47.0 polymer components (2) 130 (2) 130 (2) 130 (2)43.0 (° C.) (3) 43.0Mixing ratio of polymer (1) 0.7 (1) 0.9 (1) 0.64 (1) 0.7 components:W_(I) (2) 0.3 (2) 0.1 (2) 0.27 (2) 0.3 (3) 0.09 Parameter X (° C) 69.173.3 69.1 45.8 (B) Kind of phosphite B-3 B-3 B-3 B-3 ester compoundMixing ratio to 100 parts 2.0 2.0 2.0 2.0 by wt of polymer compounds(parts by wt.) (C) Kind of phosphite Na hypo- Ca hypo- Ca hypo- Ca hypo-metal salt phosphite phosphite phosphite phosphite Mixing ratio to 100parts 0.5 0.5 0.5 0.5 by wt of polymer component (parts by wt.) (D) Kindof molecular Adipic Adipic — Adipic weight controlling agent acid acidacid Mixing ratio to 100 parts 0.5 0.5 — 0.5 by wt of polymer component(parts by wt.) (E) Kind of other mixing GF GF GF GF material Mixingratio to 100 parts by wt of polymer 100 100 100 100 component (parts bywt.) Characteristics of block 32000 32000 40000 32000 copolymer Weightaverage molecular wt. (Mw) Number of glass 1 1 1 1 transition temp.: mGlass transition temp. 61.0 70.0 66.0 46.0 (° C.) Parameter Y 0.31 0.520.14 0.17 Melting point (°C.) 215 217 240 250 Physical properties of14.0 15.0 15.0 14.0 molding Flexural modulus (23° C.) (Gpa) Flexuralmodulus 10.0 12.0 11.5 8.5 (80° C.) (Gpa) Tensile strength (Mpa) 200 230220 220 Tensile elongation (%) 7.5 6.5 7.0 7.5 Notched Izod impact 90 8085 85 strength (23° C.) (J/m) Appearance 80 85 85 75 Color tone (valueb) −3.0 −3.0 −3.0 −3.0 Water absorption 1.15 1.00 1.00 1.35 (23° C. × 24hr) (wt. %)

[0167] TABLE 4 Example Example Example Example 12 13 14 15 (A) Polymercomponents 2 2 2 2 Number of polymer components: n Kind of polymer (1)PA66 (1) PA66 (1) PA66 (1) PA66 components (2) PET (2) PET (2) PET (2)PTT Glass transition temp. of (1) 47.0 (1) 47.0 (1) 47.0 (1) 47.0polymer components (2) 81.0 (2) 81.0 (2) 80.0 (2) 42.0 (° C.) Mixingratio of polymer (1) 0.7 (1) 0.6 (1) 0.7 (1) 0.7 components: W_(I) (2)0.3 (2) 0.4 (2) 0.3 (2) 0.3 Parameter X (° C.) 57.2 60.6 56.9 45.5 (B)Kind of phosphite B-3 B-3 B-3 B-3 ester compound Mixing ratio to 100parts 2.0 2.0 2.0 2.0 by wt of polymer component (parts by wt.) (C) Kindof phosphite Ca hypo- Ca hypo- Ca hypo- Ca hypo- metal salt phosphitephosphite phosphite phosphite Mixing ratio to 100 parts 0.5 0.5 0.5 0.5by wt of polymer component (parts by wt.) (D) Kind of molecular — — — —weight controlling agent Mixing ratio to 100 parts — — — — by wt ofpolymer component (parts by wt.) (E) Kind of other mixing GF GF GF GFmaterial Mixing ratio to 100 parts 50 50 50 50 by wt of polymercomponent (parts by wt.) Characteristics of block 32000 32000 3800032000 copolymer Weight average molecular wt. (Mw) Number of glass 2 2 21 transition temp.: m Glass transition temp. 73.1 72.5 73.0 46.5 (° C.)50.1 49.8 49.7 Parameter Y 0.68 0.69 0.71 0.67 Melting point (° C.) 230228 230 248 224 Physical properties of 8.75 8.75 8.75 8.5 moldingFlexural 8.75 modulus (23° C.) (Gpa) Tensile strength (Mpa) 150 140 150175 Tensile elongation (%) 6.8 6.3 6.8 6.8 Notched Izod impact 50 50 5060 strength (23° C.) (J/m) Appearance 65 65 65 70 Color tone (value b)−3.5 −3.5 −2.0 −3.5 Water absorption (24 hr 0.37 0.35 0.37 0.37 inwater) (wt. %) Development state of a few a few a few No cracksenvironmental stress cracks cracks cracks cracks

[0168] TABLE 5 Example Example Comp. Ex. 16 17 2 (A) Polymer components2 2 2 Nunber of polymer components: n Kind of polymer components (1)PA66 (1) PET (2) PET (2) PBT (2) PIT (2) PTT Glass transition temp. of(1) 47.0 (1) 80.0 (1) 80.0 polymer components (° C.) (2) 25.0 (2) 42.0(2) 42.0 Mixing ratio of polymer (1) 0.7 (1) 0.5 (1) 0.5 components:W_(I) (2) 0.3 (2) 0.5 (2) 0.5 Parameter X (° C.) 40.4 61.0 61.0 (B) Kindof phosphite ester B-3 B-3 — compound Mixing ratio to 100 parts by 2.02.0 — wt of polymer component (parts by wt.) (C) Kind of phosphite metalCa-hypo Ca-hypo — salt phosphite phosphite Mixing ratio to 100 parts by0.5 0.5 — wt of polymer component (parts by wt.) (D) Kind of molecularweight — — — controlling agent Mixing ratio to 100 parts by — — — wt ofpolymer component (parts by wt.) (E) Kind of other mixing GF GF GFmaterial Mixing ratio to 100 parts by 50 50 50 wt of polymer component(parts by wt.) Characteristics of block 38000 35000 35000 copolymerWeight average molecular wt. (Mw) Number of glass transition 2 1 1temp.: m Glass transition temp. (° C.) 45.5 58 60 26.0 Parameter Y 0.850.16 0.05 Melting point (° C.) 250 245 240 224 Physical properties ofmolding 8.5 9.5 8.5 Flexural modulus (23° C.) (Gpa) Tensile strength(Mpa) 210 160 130 Tensile elongation (%) 6.8 6.0 6.0 Notched Izod impactstrength 60 50 50 (23° C.) (J/m) Appearance 60 75 75 Color tone (valueb) −2.0 −3.0 18.0 Water absorption (24 hr in 0.37 0.02 0.05 water) (wt.%) Development state of No cracks No cracks Cracks environmental stresscracks occurred

[0169] TABLE 6 Example Example Example 18 19 20 (A) Polymer components 22 2 Number of polymer components: n Kind of polymer components (1) PC(1) PC (3) PC (2) PBT (2) PBT (2) PTT Glass transition temp. of (1) 150(1) 150 (1) 150 polymer camponents (° C.) (2) 25.0 (2) 25.0 (2) 42.0Mixing ratio of polymer (1) 0.3 (1) 0.5 (1) 0.3 components: W_(I) (2)0.7 (2) 0.5 (2) 0.7 Parameter X (° C.) 62.5 87.5 74.4 (B) Kind ofphosphite ester B-3 B-3 B-3 compound Mixing ratio to 100 parts by 0.50.5 0.5 wt of polymer component (parts by wt.) (C) Kind of phosphitemetal Ca hypo- Ca hypo- Ca hypo- salt phosphite phosphite phosphiteMixing ratio to 100 parts by 0.5 0.5 0.5 wt of polymer component (partsby wt.) (D) Kind of molecular weight — — — controlling agent Mixingratio to 100 parts by — — — wt of polymer component (parts by wt.) (E)Kind of other mixing — — — material Mixing ratio to 100 parts by — — —wt of polymer component (parts by wt.) Characteristics of block 2200022000 22000 copolymer Weight average molecular wt. (Mw) Number of glasstransition 2 2 2 temp.: m Glass transition temp. (° C.) 110 115 137 50.348.5 46.5 Parameter Y 0.43 0.53 0.84 Melting point (° C.) 223 220 226Physical properties of molding 2.8 2.8 2.8 Flexural modulus (23° C.)(Gpa) Flexural modulus (80° C.) (Gpa) 1.10 1.25 1.10 Tensile strength(Mpa) 67 67 67 Tensile elongation (%) 8.0 8.0 8.0 Notched Izod impactstrength 45 98 45 (23° C.) (J/m) Appearance 90 90 90 Color tone (valueb) −2.5 −2.5 −2.5

[0170] TABLE 7 Example Comp. Ex. 21 3 (A) Polymer components 2 2 Numberof polymer components: n Kind of polymer components (1) PC (1) PC (2)PBT (2) PBT Glass transition temp. of (1) 150 (1) 150 polymer components(° C.) (2) 25.0 (2) 25.0 Mixing ratio of polymer (1) 0.3 (1) 0.3components: W_(I) (2) 0.7 (2) 0.7 Parameter X (° C.) 62.5 62.5 (B) Kindof phosphite ester B-3 — compound Mixing ratio to 100 parts by 0.5 — wtof polymer component (parts by wt.) (C) Kind of phosphite metal Znphosphite — salt Mixing ratio to 100 parts by 0.5 — wt of polymercomponent (parts by wt.) (D) Kind of molecular weight — — controllingagent Mixing ratio to 100 parts by — — wt of polymer component (parts bywt.) (E) Kind of other mixing — — material Mixing ratio to 100 parts by— — wt of polymer component (parts by wt.) Characteristics of block22000 22000 copolymer Weight average molecular wt. (Mw) Number of glasstransition 2 1 temp.: m Glass transition temp. (° C.) 90.5 60.2 58.0Parameter Y 0.22 0.06 Melting point (° C.) 220 217 Physical propertiesof molding 2.8 2.8 Flexural modulus (23° C.) (Gpa) Flexural modulus (80°C.) (Gpa) 0.90 0.75 Tensile strength (Mpa) 67 67 Tensile elongation (%)8.0 8.0 Notched Izod impact strength 38 40 (23° C.) (J/m) Appearance 9090 Color tone (value b) 0.2 18.0

INDUSTRIAL UTILITY

[0171] The present block copolymer has good moldability and can besimply and economically produced from rework products or recycleproducts as raw materials. Furthermore, moldings obtained from thepresent block copolymer are distinguished in hot regidity, heatresistance, chemical resistance, surface appearance, etc.

[0172] Thus, it is expectable that the present block copolymer cansatisfy any of the requirements such as reworking or recycling of parts,and higher performance and higher functionalization of resin materialsin various applications to versatile consumer fields of packaging,containers, etc., parts for automobile exterior furnishing and sheets,parts for automobile interior furnishing, parts for automobileunderhood, parts for two-wheeler bicycles, parts for furniture, partsfor the field of OA applicances, parts for electronic appliances, partsfor industrial products, etc.

1. A block copolymer, which comprises at least two kinds of polymercomponents each having a different structural unit in the polymer, wherethe polymer components are selected from the group consisting ofpolyamide, polyester, polycarbonate and polyarylate, Y given by thefollowing formula (1) is 0.1-0.9:$Y = \left. {\frac{1}{m}\sum\limits_{j = 1}^{m}}\quad \middle| \frac{{Tg}_{j} - X}{{Tg}_{j}^{(A)} - X} \right|$

(wherein m is the number of glass transition temperatures of the blockcopolymer, Tg_(j) is the glass transition temperature (° C.) of theblock copolymer, Tg^((A)) _(j) is the glass transition temperature (°C.) of the polymer component nearest to Tg_(j) among the glasstransition temperatures of the polymer components, and X is given by thefollowing formula (2):$X = {\sum\limits_{i = 1}^{n}{{Tg}^{(B)}{iw}_{i}}}$

wherein n is the number of polymer components, Tg^((B)) _(i) is theglass transition temperatures (° C.) of the individual polymercomponents and w_(i) is the weight ratios of the individual polymercomponents).
 2. A block copolymer according to claim 1, wherein thedifference in the glass transition temperature between the polymercomponents constituting the block copolymer is 50° C. or higher.
 3. Ablock copolymer according to claim 1, wherein the block copolymer has aweight average molecular weight (Mw) of 20,000-200,000.
 4. A blockcopolymer according to claim 1, wherein the block copolymer comprises atleast two kinds of polyamides.
 5. A block copolymer according to claim1, wherein the block copolymer comprises polyamide and polyester.
 6. Ablock copolymer according to claim 1, wherein the block copolymercomprises at least two kinds of polyesters.
 7. A block copolymeraccording to claim 1, wherein the block copolymer comprises polyesterand polycarbonate.
 8. A block copolymer according to claim 1, whereinthe polyamide is selected from the group consisting of polycaprolactam,polyhexamethylene adipamide, polyhexamethylene dodecamide,polyhexamethylene isophthalamide, polyhexamethylene terephthalamide,polyhexamethylene cyclohexylamide and their copolymers.
 9. A blockcopolymer according to claim 1, wherein the polyester is selected fromthe group consisting of polyethylene terephthalate, polytrimethyleneterephthalate and polybutylene terephthalate.
 10. A block copolymeraccording to claim 1, wherein the block copolymer has an averagesequence length of 10-50 determined by nuclear magnetic resonance(¹³C—NMR).
 11. A process for producing a block copolymer, whichcomprises melt kneading (A) at least two kinds of polymer componentseach having a different structural unit in the polymer and selected fromthe group consisting of polyamide, polyester, polycarbonate andpolyarylate, with (B) a phosphite ester compound and (C) a phosphitemetal salt.
 12. A process for producing a block copolymer according toclaim 11, wherein the polymer component (A) are at least two kinds ofpolyamides.
 13. A process for producing a block copolymer according toclaim 11, wherein the polymer components (A) are polyamide andpolyester.
 14. A process for producing a block copolymer according toclaim 11, wherein the polymer components (A) are at least two kinds ofpolyesters.
 15. A process for producing a block copolymer according toclaim 11, wherein the polymer components (A) are polyester andpolycarbonate.
 16. A process for producing a block copolymer accordingto claim 11, wherein the proportion of the component (B) is 0.05-10parts by weight and the proportion of the component (C) is 0.05-10 partsby weight on the basis of 100 parts by weight of the polymer components(A).
 17. A process for producing a block copolymer according to claim11, wherein a molecular weight controlling agent (D) is further meltkneaded.
 18. A process for producing a block copolymer according toclaim 17, wherein the proportion of the component (D) is 0.05-10 partsby weight on the basis of 100 parts by weight of the polymer components(A).